Herbicidal method



United States Patent O 3,101,263 HERBICIDAL METHOD Harry Tiiles, El Cerrito, and Joe Antoguini, Mountain View, Calif., assignors to Stauffer Chemical Company, a corporation of Delaware No Drawing. Filed Apr. 20, 1959, Ser. No. 807,344 7 Claims. (Cl. 71-23) This invention relates to certain cycloalkyl esters of disuhstitutcd thioloanbamic acids as herbicides, and as new compounds. More specifically, the invention relates to compounds of the general formula:

wherein R is a cycloalkyl radical and wherein R and R are selected from the same and difieren-t lower alkyl and lower allyl radicals. Typical non-limiting examples of the various subs-tituents are as follows:

Cyclohexyl Example I (R4985 ).-6 g. (0.034 mole) of cyclo-hexyl chlorothiol-.

formate was added dropwise to a solution of 5.4 g. (0.074 mole) of diethylarni-ne in 100 cc. of ethyl ether. After standing for min, 50 cc. of water were added and the phases separated. The ether phase was then washed with 2-50 cc. portions of 5% HCl and 2-50 cc. portions of water. The organic phase was then dried over anhydrous magnesium sulfate, filtered and the filtrate was concentrated on the steam 'bath. The residual liquid was then fractionally distilled through an 18" Podbielniak Heli- Grid fractional distillation column. There was obtained 4.6 g. (63.2% yield) of cyclohexyl N,N-diethylthioloarbamate, B.P. (10 mm.) 147.0-147.1 (3., 11 1.5019.

Analysis.-Calcd. for C H -NOS: N, 6.50%. N, 6.50%. v

Example 11 Found Example 111 (R3072).When the general procedure of Example I was repeated except that 7.2 g. (0.0740 mole) of diallylamine, 6 g. (0.034 mole) of cyclohexyl chlorothiolformate and 100 cc. of ethyl ether were employed, there was obtained 4.5 g. (56.2% yield) of cyclohexyl N,N-

' there was obtained 5.2 g. (63.8% yield) of cyolohexyl N-ethyl-N-n butylth-iolearbamate, B.P. 10 mm.) 167.0

, annaaa i Patented Aug. 20, 1963 'diallylthiolcarbama-te, B.P. 10 mm.) -164.5-165.-0 C., n 1.5160. 7

Analysis.Calcd. for C H NOS: N, 5.85%. Found: N, 5.96%. Example IV (R-3073).Wthen the general procedure of Example I was repeated except that 7.3 g. (0.074 mole) of N- IallyI-n-propylar'nine, 6 g. (0.034 mole) of cycl ohexyl chlorothiolformate and 100 cc. of ethyl ether were em ployed, there was obtained 4.9 g. (60.3% yield) of cycloh'exyl -N-allyl-N-napropylthiolcarbamate, B.P. (10 mm.) 16S.0 165.5 C., 11 1.5064.

Analysis.Calcd. for C H N-OS: N, 5.80%. N, 5.79%.

Found Example V (R-3078).-When the general procedure of Example ti was repeated except that 7.5 g. (0.074 mole) of N-ethyln-butylamine, 6 g. (0.034 mole) of cyclohexyl chlorothiolfonmate and 100 cc. of ethyl ether were employed,

Analysis.Calcd. for C13H25NOS: N, 5.75 Found:

Example VI (R-3079).When the general procedure of Example -I was repeated except that 7.3 g. (0.074 mole) of N- methallylet-hylamine, 6 g. (0.034 mole) of cyclohexyl chlorothiolformate and 100 cc. of ethyl ether were employed, there was obtained 4.7 g. (58.5% yield) of cyclohexy-l N-methallyl-N-ethyl-thiolcarbamate, B.P. (10 mm.)

Analysis.Ca-lcd. for C H NOS: :N, 5.80%. N, 5.83%.

Found:

Example VII (R3083).When the general procedure of Example I was repeated except that 10.7 g. (0.11 mole) of diallylamine, 8.2 g. (0.05 mole) of cyclopentyl chlorothiolfor-mate and cc. of ethyl ether were employed, there were obtained 6.4 g. (56.9% yield) of cyclopentyl N,N- diallylthiolcarbamate, B.P. (10 mm.) 153.5154.0' C.,

Analysis.-Calcd. for C I-I NOS: N, 6.22%. Found: N, 6.24%.

' Example VIII (R-2808).When the general procedure of Example I was repeated except that 8.0 g. (0.11 mole) of diethylamine, 8.2 g. (0.05 mole) of cyclopentyl chlorothiolformate and 100 cc. of ethyl ether were employed, there was obtained 7.0 g. (69.0% yield) of cyclopentyl N,N- diethylthiolcarbamate, B.P. (10 mm.) 135.0136.'0 C., n 1.5011.

Analysis.--Calcd. for C I-I NOS: N, 6.96%. Found: N, 6.70%.

Y Example IX 3 Example X (12-3084 ).-When the general procedure of Example I was repeated except that 10.9 g. (0.11 mole) of N-allyl n-propylamine, 8.2 g. (0.05 mole) of cyclopentyl chlorothiolformate and 100 cc. of ethyl ether were employed, there was obtained 7.6 g. (67.1% yield) of cyclopentyl N-allyl-N-n-propylthiolcarbamate, B.P. (10 mm.) 153.0- 153.5 C., 11 1.5053.

Analysis.-Calcd. for C I-1 N051 N, 6.16%. Found: N, 6.23%.

Example XI (I-Z3091).-When the general procedure of Example I was repeated except that 11.1 g. (0.11 mole) of N-ethyln-butylamine, 8.2 g. (0.05 mole) of cyclopentyl chlorothiolformate and 100 cc. of ethyl ether were employed, there was obtained 8.4 g. (73.2% yield) of cyclopentyl N-ethyl-N-n-butylthiolcarbamate, B.P. 10 mm.) 157.0- 158.0-.C., 11 1.4953.

2 Growth.

The above tests were then repeated using application rates of 10 and 40 pounds per acre with the following results:

1 Percent germination.

- 1 Peas Corn Radish Oats Cucumber Compound Lbs./

acre

Ge. Gr. Gc. Gr. Ge. Gr. Ge. Gr. Ge. Gr.

10 100 7 100 10 100 10 10 0+ 100 9 40 100 3 100 9 100 10 0 100 5 100 10 100 10 100 10 60 0+ 100 10 40 100 10 100 10 100 10 20 0+ 100 10 10 100 10 100 10 100 10 100 l 100 10 40 100 10 100 10 100 10 00 0+ 100 10 10 100 10 100 10 100 10 100 1 100 10 40 100 10 100 10 100 10 00 0+ 100 10 10 100 10 100 10 100 10 00 2 100 10 40 100 7 100 8 100 9 l0 1 100 10 10 100 8 100 10 100 8 100 0+ 100 i 10 40 100 6 100 10 100 7 5 0+ 100 l0 10 100 5 100 10 100 10 100 0+ 100 9 40 100 2 100 5. 5 100 7. 5 30 0+ 0 10 100 4 100 10 100 10 100 0+ 100 10 40 100 3 100 7. 5 100 7 0 5 10 100 3 100 8 100 9 10 0+ 100 10 40 100 2 100 8 50 4 5 0+ 100 8 10 100 5 100 10 100 10 30 0+ 100 4 40 100 1 100 10 4 0 o. 20 0+ 10 60 4 100 10 100 10 20 0+ 5 40 2 100 7 100 10 0 l0 1 10 100 3 100 10 100 10 20 0+ 100 7 40 20 1 100 10 100 7 0 100 5 1 Percent germination. 2 Growth.

Analysis.Calcd. for C H NOS: N, 6.11%. Found: N, 6.10%.

Example XII (22-3092) .--When the general procedure of Example I was repeated except that 109g. (0.11 mole) of N-methallylethylamine, 8.2 g. (0.05 mole) of cyclopentyl chlorothiolformate and 100 cc. of ethyl ether were employed, there was obtained 8.5 g. (74.9% yield) of cyclopentyl N-methallyl-N-ethylthiolcarbamate, 13.1. (10 mm.) 1495-1500 C., 11, 1.5063.

Analysis.-Calcd. for C H NOS: N, 6.16%. Found: N, 6.05%.

The compounds of the present invention have been 'tested as herbicides and found very eifective as the following typical tests show. Some of the compounds are quite selective in their action and can be used to eradicate or control one type of plant, while another type of plant is relatively unafiected.

In making the following tests, seeds were planted in 3" pots and shortly thereafter the compound under test was applied to the pots in a drench at'the rate of 365 pounds per acre. The pots were placed in a greenhouse and watered at suitable intervals and the germination and growth of the seeds was compared with similarly planted seeds to which no herbicide was added. In each case, germination (Germ. or Ge.) was reported on the scale of 0100%, while growth (Gn) was reportedon the scale of 0-10, based on the seeds which germinated.

Thus, 100-10 indicates normal germination and normal growth.

The compounds of the present invention may be used in preemergence or postemergence herbicides and may be applied in a variety of ways at various concentrations. They may be combined with suitable carriers and applied as dusts, sprays or drenches. The amount applied will depend on the nature of the seeds or plants to be controlled .and the rate of application may vary from 1 to 500 pounds per acre. One particularly advantageous way of applying the compounds is as a narrow band along a row crop, straddling the row.

We claim:

1. The method of combating weeds comprising applying a pliy-totoxic amount to the soil of a compound:

l Ri-S-C-N 7. The method of claim 1 wherein the compound is cyclohexyl N-Z-methyl-allyl-N-ethylthiolcarbamate.

References Cited in the file of this patent UNITED STATES PATENTS Hunt et a1. Nov. 10, 1936 Loane et a1. June 6, 1939 Baumgarmer July 24, 1951 Weijl-ard et a1. June 16, 1953 Kosrnin Aug. 24, 1954 Tilles et a1 Aug. 25, 1959 Tilles et a1. Aug. 25, 1959 6 2,913,327 Tilles et a1; Nov. 17, 1959 2,916,370 Tilles et a1 Dec. 8, 1959 2,941,879 Goodhue June 21, 1960 2,992,091 Harman et a1. July 11, 1961 5 OTHER REFERENCES Gentuer et a1.: An Evaluation of Several Chemicals for Their Herbicidal Properties, January 195 8, pages 5, I 6, and 10, U .S. Agr-ic. Research Service, Crops Research 10 Div.

Davies et aL: in Biochemical Journal, vol. 40, 1946', pages 331334. 

1. THE METHOD OF COMBATING WEEDS COMPRISING APPLYING A PHYTOTOXIC AMOUNT TO THE SOIL OF A COMPOUND: 